Photodefinable alignment layers for chemical assisted patterning and approaches for forming photodefinable alignment layers for chemical assisted patterning are described. An embodiment of the invention may include disposing a chemically amplified resist (CAR) material over a hardmask that includes a switch component. The CAR material may then be exposed to form exposed resist portions. The exposure may produces acid in the exposed portions of the CAR material that interact with the switch component to form modified regions of the hardmask material below the exposed resist portions.